Diastereoselective insertion of isocyanide into the alkyl metal bond of methylbenz[e]indenyl ansa-zirconocene complexes

Alkylation of ansa-zirconocene [Zr{(η5-C5H5)SiMe2(MBI)}Cl2] (MBI = η5-2-Me−C13H7) with MgRCl gave the dimethyl complex [Zr{(η5-C5H5)SiMe2(MBI)}Me2], but unresolvable mixtures containing mono-alkylated compounds were obtained when bulkier alkyls were used. However pure dialkyl complexes [Zr{(η5-C5H5)...

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Detalles Bibliográficos
Autores: Sebastián Navas, Alfredo, Royo Gracia, Pascual, Gómez Sal, Pilar|||0000-0002-9279-210X, Ramírez de Arellano, Carmen
Tipo de recurso: artículo
Fecha de publicación:2004
País:España
Institución:Universidad de Alcalá (UAH)
Repositorio:e_Buah Biblioteca Digital Universidad de Alcalá
Idioma:inglés
OAI Identifier:oai:ebuah.uah.es:10017/4180
Acceso en línea:http://hdl.handle.net/10017/4180
https://dx.doi.org/10.1002/ejic.200400333
Access Level:acceso abierto
Palabra clave:Metallocenes
Zirconium
Insertion
Isocyanides
Polymerization
Ciencia
Química inorgánica
Science
Chemistry, inorganic
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spelling Diastereoselective insertion of isocyanide into the alkyl metal bond of methylbenz[e]indenyl ansa-zirconocene complexesSebastián Navas, AlfredoRoyo Gracia, PascualGómez Sal, Pilar|||0000-0002-9279-210XRamírez de Arellano, CarmenMetallocenesZirconiumInsertionIsocyanidesPolymerizationCienciaQuímica inorgánicaScienceChemistry, inorganicAlkylation of ansa-zirconocene [Zr{(η5-C5H5)SiMe2(MBI)}Cl2] (MBI = η5-2-Me−C13H7) with MgRCl gave the dimethyl complex [Zr{(η5-C5H5)SiMe2(MBI)}Me2], but unresolvable mixtures containing mono-alkylated compounds were obtained when bulkier alkyls were used. However pure dialkyl complexes [Zr{(η5-C5H5)SiMe2(MBI)}R2] (R = CH2Ph, CH2SiMe3) were easily obtained using K(CH2Ph) and Li(CH2SiMe3) as alkylating agents. Diastereoselective insertion into the MBI-unprotected Zr−R bond was observed when all of these dialkyl complexes were treated with 2,6-xylyl isocyanide to give the iminoacyl compounds [Zr{(η5-C5H5)SiMe2(MBI)}R{CR[η2-N-(2,6-xylyl)]}] (R = Me, CH2Ph, CH2SiMe3). All of the new complexes were characterized by NMR spectroscopy and the X-ray molecular structures of the dibenzyl and the imino-benzyl compounds were determined. The catalytic activity for ethene polymerization and ethene/1-hexene copolymerization of the dichloro zirconocenes [Zr{(η5-C5H5)EMe2(MBI)}Cl2] (E = C, Si), activated with methylalumoxane (MAO), was measured.Comisión Asesora de Investigación Científica y TécnicaJohn Wiley & Sons20042004-01-01journal articlehttp://purl.org/coar/resource_type/c_6501NAhttp://purl.org/coar/version/c_be7fb7dd8ff6fe43info:eu-repo/semantics/articleapplication/pdfhttp://hdl.handle.net/10017/4180https://dx.doi.org/10.1002/ejic.200400333reponame:e_Buah Biblioteca Digital Universidad de Alcaláinstname:Universidad de Alcalá (UAH)InglésengCAICYT Not available MAT2001-1309 Síntesis y estudio de catalizadores selectivos para la producción de materiales poliolefÍnicos con propiedades predeterminadasopen accesshttp://purl.org/coar/access_right/c_abf2Attribution-NonCommercial-NoDerivatives 4.0 Internationalhttp://creativecommons.org/licenses/by-nc-nd/4.0/info:eu-repo/semantics/openAccessoai:ebuah.uah.es:10017/41802026-06-18T11:13:07Z
dc.title.none.fl_str_mv Diastereoselective insertion of isocyanide into the alkyl metal bond of methylbenz[e]indenyl ansa-zirconocene complexes
title Diastereoselective insertion of isocyanide into the alkyl metal bond of methylbenz[e]indenyl ansa-zirconocene complexes
spellingShingle Diastereoselective insertion of isocyanide into the alkyl metal bond of methylbenz[e]indenyl ansa-zirconocene complexes
Sebastián Navas, Alfredo
Metallocenes
Zirconium
Insertion
Isocyanides
Polymerization
Ciencia
Química inorgánica
Science
Chemistry, inorganic
title_short Diastereoselective insertion of isocyanide into the alkyl metal bond of methylbenz[e]indenyl ansa-zirconocene complexes
title_full Diastereoselective insertion of isocyanide into the alkyl metal bond of methylbenz[e]indenyl ansa-zirconocene complexes
title_fullStr Diastereoselective insertion of isocyanide into the alkyl metal bond of methylbenz[e]indenyl ansa-zirconocene complexes
title_full_unstemmed Diastereoselective insertion of isocyanide into the alkyl metal bond of methylbenz[e]indenyl ansa-zirconocene complexes
title_sort Diastereoselective insertion of isocyanide into the alkyl metal bond of methylbenz[e]indenyl ansa-zirconocene complexes
dc.creator.none.fl_str_mv Sebastián Navas, Alfredo
Royo Gracia, Pascual
Gómez Sal, Pilar|||0000-0002-9279-210X
Ramírez de Arellano, Carmen
author Sebastián Navas, Alfredo
author_facet Sebastián Navas, Alfredo
Royo Gracia, Pascual
Gómez Sal, Pilar|||0000-0002-9279-210X
Ramírez de Arellano, Carmen
author_role author
author2 Royo Gracia, Pascual
Gómez Sal, Pilar|||0000-0002-9279-210X
Ramírez de Arellano, Carmen
author2_role author
author
author
dc.subject.none.fl_str_mv Metallocenes
Zirconium
Insertion
Isocyanides
Polymerization
Ciencia
Química inorgánica
Science
Chemistry, inorganic
topic Metallocenes
Zirconium
Insertion
Isocyanides
Polymerization
Ciencia
Química inorgánica
Science
Chemistry, inorganic
description Alkylation of ansa-zirconocene [Zr{(η5-C5H5)SiMe2(MBI)}Cl2] (MBI = η5-2-Me−C13H7) with MgRCl gave the dimethyl complex [Zr{(η5-C5H5)SiMe2(MBI)}Me2], but unresolvable mixtures containing mono-alkylated compounds were obtained when bulkier alkyls were used. However pure dialkyl complexes [Zr{(η5-C5H5)SiMe2(MBI)}R2] (R = CH2Ph, CH2SiMe3) were easily obtained using K(CH2Ph) and Li(CH2SiMe3) as alkylating agents. Diastereoselective insertion into the MBI-unprotected Zr−R bond was observed when all of these dialkyl complexes were treated with 2,6-xylyl isocyanide to give the iminoacyl compounds [Zr{(η5-C5H5)SiMe2(MBI)}R{CR[η2-N-(2,6-xylyl)]}] (R = Me, CH2Ph, CH2SiMe3). All of the new complexes were characterized by NMR spectroscopy and the X-ray molecular structures of the dibenzyl and the imino-benzyl compounds were determined. The catalytic activity for ethene polymerization and ethene/1-hexene copolymerization of the dichloro zirconocenes [Zr{(η5-C5H5)EMe2(MBI)}Cl2] (E = C, Si), activated with methylalumoxane (MAO), was measured.
publishDate 2004
dc.date.none.fl_str_mv 2004
2004-01-01
dc.type.none.fl_str_mv journal article
http://purl.org/coar/resource_type/c_6501
NA
http://purl.org/coar/version/c_be7fb7dd8ff6fe43
dc.type.openaire.fl_str_mv info:eu-repo/semantics/article
format article
dc.identifier.none.fl_str_mv http://hdl.handle.net/10017/4180
https://dx.doi.org/10.1002/ejic.200400333
url http://hdl.handle.net/10017/4180
https://dx.doi.org/10.1002/ejic.200400333
dc.language.none.fl_str_mv Inglés
eng
language_invalid_str_mv Inglés
language eng
dc.relation.none.fl_str_mv CAICYT Not available MAT2001-1309 Síntesis y estudio de catalizadores selectivos para la producción de materiales poliolefÍnicos con propiedades predeterminadas
dc.rights.none.fl_str_mv open access
http://purl.org/coar/access_right/c_abf2
Attribution-NonCommercial-NoDerivatives 4.0 International
http://creativecommons.org/licenses/by-nc-nd/4.0/
dc.rights.openaire.fl_str_mv info:eu-repo/semantics/openAccess
rights_invalid_str_mv open access
http://purl.org/coar/access_right/c_abf2
Attribution-NonCommercial-NoDerivatives 4.0 International
http://creativecommons.org/licenses/by-nc-nd/4.0/
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
dc.publisher.none.fl_str_mv John Wiley & Sons
publisher.none.fl_str_mv John Wiley & Sons
dc.source.none.fl_str_mv reponame:e_Buah Biblioteca Digital Universidad de Alcalá
instname:Universidad de Alcalá (UAH)
instname_str Universidad de Alcalá (UAH)
reponame_str e_Buah Biblioteca Digital Universidad de Alcalá
collection e_Buah Biblioteca Digital Universidad de Alcalá
repository.name.fl_str_mv
repository.mail.fl_str_mv
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